The instant invention is directed to 1-hydroxymethyl-2-acyl cyclopropane derivatives having the generic structure: ##STR2## wherein Z represents hydrogen, acyl having the structure: ##STR3## and substituted oxyacyl having the structure: ##STR4## and cyclic condensation products thereof having the structure: ##STR5## wherein R.sub.1, R.sub.2 and R.sub.3 represent C.sub.1 -C.sub.10 alkyl; wherein R.sub.1 ' is C.sub.1 -C.sub.10 alkylidene; and wherein R.sub.4, R.sub.5, R.sub.6 and R.sub.7 represent hydrogen or C.sub.1 -C.sub.3 lower alkyl,
processes for preparing same involving the reaction of halo methyl oxirane derivatives defined according to the structure: ##STR6## wherein X represents chloro, bromo or iodo with substituted 1,3-propanediones having the structure: ##STR7## and organoleptic uses thereof in augmenting or enhancing the aroma or taste of consumable materials.
There has been considerable work performed relating to substances which can be used to impart (or alter, modify or enhance) flavors and fragrances to (or in) various consumable materials. These substances are used to diminish the use of natural materials, some of which may be in short supply and to provide more uniform properties in the finished product.
Sweet, green, herbaceous, fruity, pineapple, grapefruit-like, leathery, coconut-like, and jasmine-like aromas with mushroom-like and anisic undertones are particularly desirable in several types of perfume compositions and for use in perfumed articles and colognes.
Sweet, fruity, fresh pineapple-like, fresh grapefruit-like, coconut-like and mushroom-like aroma and taste nuances are particularly desirable for many uses in foodstuff flavors, particularly tropical fruit flavors.
Compounds containing carbonyl functions and cyclopropyl moieties are known for use in the art of perfumery and flavors. Thus, substituted cyclopropane derivatives such as ethyl chrysanthemumate(2,2-dimethyl-3-(2-methylpropenyl)cyclopropane carboxylic acid, ethyl ester) having the structure: ##STR8## is disclosed as Compound 487 in "Perfume and Flavor Chemicals (Aroma Chemicals)" Volume 1, Arctander published 1969 as having a powerful, winey, herbaceous, sweet and ethereal, very pleasant odor of intriguing complexity. Arctander states that this material has spicy-herbaceous, warm and almost green-floral notes which resemble certain notes in a jasmine complex. However, no indication exists that this type of compound augments or enhances the nuances stated in the instant application.
Furthermore, U.S. Pat. No. 3,926,860 issued on Dec. 16, 1975 (the disclosure of which is incorporated by reference herein) states that as a result of analyzing natural patchouli oil, it was found that cis-2-n-pentylcyclopropane-1-carboxylic acid having the structure: ##STR9## is a key component for patchouli fragrance having a patchouli-like, animal, leathery note and having the capability of imparting such notes to perfumes and cosmetic compositions. The compound having the structure: ##STR10## is indicated to have fragrance properties which are surprisingly different in kind from other known compounds and compositions in the "prior art", to wit:
i. Beilstein, Volume E III 9, page 101 disclosing 2-n-hexyl-cyclopropane-carboxylic acid-(1) (no disclosure of aroma); PA1 ii. Snejkal et al., Collection Czech. Chem. Communications 25, 1746-50 (1960) discloses interalia, cis-isobutyl cyclopropane carboxylic acid (no disclosure of aroma); PA1 iii. Danilkina and D'yakonov, Zh. Obshch. Khin., 34 (9) 3129-30 (1964) discloses 2-butyl cyclopropane carboxylic acid (cis/trans mixture with no aroma disclosed); PA1 iv. Dolgii et al., Farmakol. Toksikol. 30(2), 199-203 (1967) discloses 2-n-pentylcyclopropane carboxylic acid (no reference made to isomeric configuration of to aroma); PA1 v. D'yakonov et al., Zh. Obschei. Khim. 35, 2169 (1965) discloses mixtures of cis and trans-2-pentylcyclopropane carboxylic acid, the trans acid being in the major proportion. No reference is made to aroma; PA1 vi. Julia et al. Bull Soc. Chim. France 1970, 1805 discloses cis-2-n-butyl cyclopropane carboxylic acid ethyl ester at page 1808 without reference being made to its aroma.
The 1-hydroxymethyl-2-acyl cyclopropane derivatives of the instant invention have chemical structures and properties different in kind from the chemical structures and properties of the compounds of the prior art.
Furthermore, the processes for producing the 1-hydroxymethyl-2-acyl cyclopropane derivatives of our invention are novel. Organic Synthesis, Volume IV, John Wiley & Sons Publishing Company, 1969 at page 597 discloses a technique for making acyl cyclopropane derivatives according to the reaction sequence: ##STR11## but the mechanism of our invention is neither expressly nor implicitly set forth therein.
Indeed, the prior art teaches away from our invention as is seen by Mesropyan et al. at Chem. Abstracts, Volume 78, 1973, 135590y which teaches the reaction: ##STR12## and further, as seen by Arbuzov et al. Volume 80, 1974, Chem. Abstracts 47884h which teaches the reaction: ##STR13##
Indeed, no rearrangement of the cyclopropyl moiety occurs when reacting the epichlorohydrin with a difunctional moiety as is shown in the reaction: ##STR14## disclosed in Chem. Abstracts 137316n, Volume 78, 1973 (abstract of South African Pat. No. 7107,767).